Cracking with catalytically active amorphous silica

ABSTRACT

Catalytically active amorphous silicas are prepared by dehydrating a silica hydrogel or precipitate prepared from an acidified aqueous silicate solution containing an amine of pK a  above 10 or a cation containing either a nitrogen or phosphorus silica is catalytically active for, among other chemical reactions, the isomerization of ortho-xylene and the cracking of hydrocarbons.

RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 356,351, filed Mar. 9, 1982 now U.S. Pat. No. 4,414,137.

BACKGROUND OF THE INVENTION

This invention relates to amorphous silica and most especially to silicagels useful in catalysis. The invention also relates to a method forpreparing such silica gels, and to catalytic processes wherein the gelsare utilized as catalysts or catalyst components.

Silica gel is but one of several forms of amorphous silica and, like theother forms, is an essentially anhydrous polymer of silica. Silica gelmay be prepared in a number of ways, one of which is to form an aqueoussilicate solution, usually an aqueous sodium silicate solution, followedby acidifying the solution to form a silica hydrogel, which, upondrying, yields a silica gel (or silica xerogel) product. Alternatively,one may form the gel by removal of the cation associated with thesilicate anion by ion exchange, followed by drying of the resultanthydrogel.

The formation of the hydrogel, by ion exchanging, acidifying, orotherwise destabilizing an aqueous silicate solution, is caused by apolymerization reaction that may be visualized as the formation of asilica network which envelops water like a sponge. Upon heating, thewater is removed, leaving microscopic cavities or pores in the locationsformerly occupied by water. The resulting product, termed either asilica gel or silica xerogel, is highly useful, as for example as anadsorbent in gas masks or as a desiccant.

As is the case with many crystalline siliceous materials, such asmordenite or Zeolite Y described in U.S. Pat. No. 3,130,007, silica gelis known as a catalyst component. However, unlike these crystallinematerials, silica gel is not itself catalytically active. Instead,silica gel is most frequently used in catalysts as a relatively inertsupport material upon which any of a number of catalytically activemetals are deposited.

Despite its usual inertness, some attempts have been made to producereactive silicas. Among these are the achievements of M. J. D. Low andH. Mark, who have authored several articles directed to silicas ofimproved chemisorption properties produced by treating conventionalsilicas with various chemical agents (for instance, trimethoxymethaneand certain dienes). The articles of Low and Mark relating to reactivesilicas include "Reactive Silica VIII. Methoxylation of Silica UsingTrimethoxymethane" set forth in the Journal of Catalysis, Vol. 44, pp.300 to 305 (1976), "Reactive Silica X. Ethylene Sorption andPolymerization" set forth in the Journal of Catalysis, Vol. 48, pp. 104to 110 (1977), and "Reactive Silica XII. The Sorption and Polymerizationof Several Alkenes" set forth in the Journal of Catalysis, Vol. 50, pp.373 to 378 (1977). M. J. D. Low has also authored a paper relative toreactive silicas in conjunction with A. G. Severdia entitled "ReactiveSilica XIII. Activation of Silica by Pyrolizing Chemisorbed HSiCl₃ " asset forth in the Journal of Catalysis, Vol. 54, pp. 219 to 222 (1978).

The efforts of the art with respect to silica gels have not resulted ina commercially attractive silica gel having highly catalytic properties.From the viewpoint of commercial preparation, it would be especiallydesirable if not only a silica gel of highly active catalytic propertieswere available but also a method of preparing such a silica gel withoutresorting to either expensive and/or corrosive chemicals or preparationsinvolving conversion of inactive silica gels to a catalytically activeform. More specifically, it would be desirable if a direct preparationmethod were available for producing a catalytically active silica gelwithout the necessity for the intermediate formation of an inactivesilica gel.

Accordingly, it is a major object of the present invention to prepare anovel amorphous silica of high catalytic activity, particularly in theform of silica gel, and to do so directly, without the necessity forconverting an inactive silica gel to an active form. It is a furtherobject of the invention to provide chemical processes wherein the silicagel of the invention is utilized to catalytically promote one or morechemical reactions. It is yet another object of the invention to preparethe silica gel of the invention with relatively inexpensive andnoncorrosive chemicals. It is yet another object to provide a novelsilica hydrogel, which, upon heating, or upon washing followed byheating, yields the catalytically active silica gel of the invention.These and other objects will become more apparent to those skilled inthe art in light of the following description of the invention.

SUMMARY OF THE INVENTION

It has now been discovered that highly catalytically active amorphoussilicas are derivable from a reaction mixture containing as theessential ingredients water, silicate anions, and an organic reactantselected from the group consisting of amines having a pK_(a) above 10,quaternary ammonium cations and quaternary phosphonium cations wherein anitrogen or phosphorus atom, respectively, is bonded to four carbonatoms, precursors of the foregoing, and mixtures thereof. Under suitableconditions, the reaction mixture yields a hydrogel or precipitate ofsilica, from which the amorphous silica of the invention may be producedby drying or calcining if the hydrogel or precipitate is relatively freeof deleterious alkali or alkaline earth metals, or, if not, the desiredsilica may be produced by removing the deleterious metals and thendrying or calcining.

The amorphous silica of the invention is useful in catalysis,particularly where the promotion of acid-catalyzed chemical reactions isrequired, as for example in the cracking of hydrocarbons or theisomerization of o-xylene. The catalytic properties of the presentsilica may be enhanced by the addition of other catalytic agents, as forexample by admixture with a zeolite or impregnation of a metalcomponent.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is, in its preferred embodiment, directed tohighly catalytically active silica gels prepared from certain aqueoussilicate reaction mixtures. The initial aqueous solution containssilicate anions, usually and most conveniently prepared by dissolvingsodium silicate in an aqueous liquid, such as distilled or deionizedwater. Other water-soluble silicate anion precursors may be used, as forexample, potassium silicate. In addition, ammonium silicate is asuitable precursor and may be prepared by ammonium ion-exchanging asolution of sodium or potassium silicate utilizing known ion exchangetechniques. Other sources of silicates may also be employed, and, ingeneral, water-soluble mono-silicates and polysilicates will proveuseful, and so also will mono- and polysilicic acids, as will variousmixtures of silicates and/or silicic acids.

The aqueous solution is generally prepared so as to have a concentrationof silicate ions such that the maximum possible amount of silicaproducible therefrom is about 2 to 30 percent by weight, calculated asSiO₂, preferably from 5 to about 15 percent by weight. A most convenientand highly preferred silicate solution is prepared by diluting N Brandsodium silicate obtainable from the Philadelphia Quartz Company withwater in a volumetric ratio between about 1:3 and 1:6, N Brand solutionto water.

In addition to water and silicate anions, the reaction mixture isfurther provided with an organic reactant selected from the groupconsisting of the amines of pK_(a) above 10, quaternary ammonium cationswherein a nitrogen atom is bonded to four carbon atoms, quaternaryphosphonium cations wherein a phosphorus atom is bonded to four carbonatoms, precursors of the foregoing and mixtures thereof. The more usefulorganic reactants added to the silicate solution are readily soluble inwater, but even reactants which are only slightly soluble in water areeffective, especially when a suitable emulsifying agent is added to thereaction mixture followed by vigorous stirring.

Suitable organic reactants for use in the invention include, forexample, ethylenediamine and pyrrolidine, but far more preferable areorganic reactants which introduce into the reaction mixture a quaternaryammonium ion wherein a nitrogen atom is bonded to four carbon atoms. Themore preferred quaternary ammonium ions contain four alkyl groups linkedto a nitrogen atom, and more preferably still, all four alkyl groupscontain between one and six carbon atoms, and most preferably betweentwo and four carbon atoms, with the most preferred alkyl groups beingn-propyl and n-butyl. In a specific embodiment of the invention,quaternary ammonium cations are introduced into the reaction mixturethrough the aid of precursors, usually by the addition of one or morealkyl salts containing one to four carbon atoms plus a tertiary aminecontaining a nitrogen atom bonded to three alkyl groups each havingbetween one and six carbon atoms. For example, in the preferredembodiment, the quaternary ammonium ions are produced by adding n-propylbromide, n-butyl bromide, and tri-n-propylamine to the reaction mixture.Alternatively, however, and assuming a relatively high pH in thereaction mixture (e.g., above about 10), the required quaternaryammonium cation may be produced by adding either ammonia or a primary orsecondary amine to the reaction mixture, along with one or more alkylcompounds, such as an alkylhalide, an alkylsulfate, etc. In yet anotherembodiment of the invention, the quaternary ammonium ions are producedvia addition of a water-soluble quaternary ammonium compound, as forexample by the addition of a compound containing a chloride, bromide,iodide, or sulfate anion and, as the cation, tetramethylammonium ion,tetraethylammonium ion, a tetrapropylammonium ion, a tetrabutylammoniumion, a diethyldipropylammonium ion, a triethylmonobutylammonium ion, andsimilar quaternary ammonium cations. One such water-soluble quaternaryammonium compound is prepared in an aqueous alkaline liquid by adding asource of ammonium and/or alkylated ammonium cations, plus sufficient ofone or more alkylhalides to replace all the hydrogen atoms, if any,which are attached to the nitrogen atom of the ammonium or alkylatedammonium cations, from which a tetraalkylammonium hydroxide isrecovered.

The reaction mixture of water, silicate anion, and organic reactant maybe prepared in any convenient manner, there being no criticality in theorder of mixing. The reaction mixture, however, will generally containbetween 20 and 200 moles of water, and preferably between 40 and 100moles of water, per atom of silicon present in the form of mono- andpolysilicic acids and mono- and polysilicates. In addition, the molarratio of water to nitrogenous reactants plus phosphorous reactantsranges from 50 to 1 to 500 to 1, preferably from 100 to 1 to 250 to 1,the reactants being the amines or quaternary cations specifiedhereinbefore, or their precursors.

The reaction mixture containing the silicate anion and suitable organicreactant(s) is, in the preferred embodiment, further provided with anorganic solvent having mutual solubility with respect to water and theorganic reactant(s). Typically, an oxygenated organic solvent isutilized for this purpose, with methylethylketone being preferred. Theamount of the methylethylketone or other organic solvent added to thereaction mixture is between about 0 and 0.10 moles per mole of water,preferably between 0.002 and 0.010 moles per mole of water.

The addition of an organic solvent is especially appropriate when one ormore of the reactants added to the reaction mixture are not readilysoluble in water. For example, most alkyl halides are only slightlysoluble in water, and an added organic solvent, such asmethylethylketone, serves as an emulsifying agent, hastening thedissolution of alkyl halide reactants, particularly when accompanied byvigorous agitation.

The formation of a hydrogel from the reaction mixture is most readilyfavored at a pH below 12.0, usually in a range of 8 to 12, preferably 10to 12. Accordingly, if the pH of the mixture is not favorable forreaction, then a suitable alkaline or acidic agent is added to drive thepH into the desired range. For example, if the reaction mixtureinitially has a pH above about 12, the chemical reactions producing thegel are favored by lowering the pH below 12, as for example, byintroduction of an acid (i.e., acidification) or by ion exchange of somemetal or ammonium cations in the reaction mixture for hydrogen ions.

Once the reaction mixture is at a suitable pH, initiation of thechemical reactions producing the hydrogel is commenced, which reactionsare believed to involve polymerization and condensation mechanisms.However, to avoid the formation of a crystalline product, the reactionmixture should be maintained under relatively low temperature conditionsfavoring the formation of at least some amorphous hydrogel product, andpreferably so as to obtain a product consisting essentially of anamorphous hydrogel. In order to achieve these results, temperatureconditions are normally maintained below about 100° C., and are usuallymaintained at temperatures above 0° but below about 100° C., with thetemperature usually being maintained between 20° and 95° C., andpreferably between 50° and 85° C.

After adjusting the pH to a desired value, the reaction mixture is ageda sufficient length of time to allow a gel to form in a mother liquor,usually by syneresis. The time required for aging is dependent on anumber of factors, including the temperature of reaction, the nature andconcentration of the ingredients in the reaction mixture, and the pH ofthe reaction mixture. Usually, under pH conditions between 10 and 12, atleast ten hours are required for gel formation, and time periods of 24to 200 hours are typical while 48 to 100 are most usual.

After the hydrogel is prepared by the foregoing or equivalent methods,it is separated from the mother liquor, as by filtration, and ifprepared from a reaction mixture rich in alkali or alkaline earth metalcations, the hydrogel is washed free of such metals, for example, bywashing with an ammonium salt solution. The metals may also be removedby other methods, but however the removal is carried out, the resultingmetals content, and particularly the alkali metals content, of thehydrogel is such that, upon dehydration, the contained metals will notinterfere with the formation of the desired silica gel, and mostespecially, with its desired catalytic activity. In general, thehydrogel is washed such that no more than 0.010 atoms of total alkalimetal remain for each atom of silicon. (Of course, one can avoid theremoval of metals entirely by initiating the chemical reactionsproducing the hydrogel in a metals-free reaction mixture, but usuallythis is far less convenient than preparation in, for example, a solutioncontaining dissolved sodium silicate.)

Subsequent to preparation of the hydrogel, it is dried and/or calcinedso as to produce the silica gel of the invention by dehydration. In thepreferred embodiment of the invention, the dehydration is effectuated bycalcining the hydrogel at temperatures above 900° F. for twenty minutesto two hours. The resulting silica gel product is, preferably,essentially completely amorphous, is usually granular, and generally hasa surface area between about 75 and 350 m² /gm, with even higher surfaceareas falling within the scope of the invention. In addition, the silicagel has a total metal to silicon atom ratio similar to that of thewashed hydrogel, and usually also a similar distribution of metals, sothat the alkali metal to silicon atom ratio of the washed hydrogel andthat of the silica gel will be substantially the same.

The silica gel of the present invention has been found to have highcatalytic activity with respect to the promotion of organic chemicalreactions, as for example, in isomerizing ortho-xylene to para-xyleneand meta-xylene and in cracking hydrocarbons into product hydrocarbonsof lower average molecular weight and lower average boiling point.Although the invention is not limited to any theory of operation, thesecatalytic properties are believed due to the presence of strong acidicsites on the gel surface, which in turn is believed due to the presenceof far fewer silanol groups on the gel surface than is the case with therelatively inactive amorphous silicas of the prior art. The paucity ofsilanol groups is also believed to impart hydrophobic and oil-adsorptionproperties, as for example from contaminated waters, to the amorphoussilicas of the invention.

Although the present silica gel may be used for catalytic purposeswithout the further addition of catalytic agents, it is often desirableto combine an active component with the present silica gel and in sodoing increase its suitability for a particular catalytic process. Forexample, if increased cracking activity is required, the silica gel canbe admixed with a cracking component, as by dispersing into the gel ahydrogen Y zeolite containing one or more stabilizing rare earthelements. In this embodiment of the invention, the zeolite, usually inpowder form, is mulled into the hydrogel from which the silica gel ofthe invention is to be subsequently obtained by dehydration or bywashing followed by dehydration. Alternatively, if hydrogenationactivity is required, a suitable Group VIB and/or Group VIII metalcomponent may be deposited on the silica gel, typically by impregnationfollowed by consecutive calcination and sulfiding treatments to producea catalyst having hydrocracking activity. To improve the hydrocrackingproperties, the catalyst may contain both a suitable hydrogenationcomponent and a zeolite in addition to the silica gel. Forhydrocracking, a stabilized Y zeolite will generally be a preferredchoice, and for a selective form of hydrocracking known ashydrodewaxing, wherein the catalyst is especially selective for crackingstraight chain and slightly branched chain paraffins, one may utilize aZSM-5-type zeolite, or, more preferably, one may employ a non-zeoliticmaterial known as silicalite, a crystalline silica polymorph disclosedin U.S. Pat. No. 4,061,724, herein incorporated by reference in itsentirety. Silicalite is especially useful for hydrodewaxing when used inconjunction with nickel-tungsten hydrogenation components.

It is especially preferred in the preparation of catalysts from thesilica gel of the invention that the silica gel be admixed with suitablebinding agents to produce sols, pastes, or slurries from which catalyticparticulates of sufficient strength and abrasion resistance for use inlarge reactor vessels may be produced. Examples of suitable bindersinclude aluminas, silicas, and clays. Especially preferred, however, arepeptized boehmite, acid-washed clays, and silicas such as bentonite,montmorillomite, halloysite, attapulgite, and magadiite. These binderscan be combined with the catalytically active silica of the invention bymulling or slurrying followed by extruding or spray drying. Furthercatalytic components, such as a Group VIB metal and/or Group VIII metalcomponent added for hydrogenation activity, may be incorporated with thebinder-active silica mixture. This may be accomplished by directaddition of a suitable precursor of the desired metal catalyticcomponent to the mulled or slurried mixtures followed by shaping andcalcination; alternatively, the binder-active silica mixture may firstbe shaped and then successively calcined, impregnated with the chosenprecursor or precursors, and calcined again. Yet other catalyticcomponents may be incorporated into the binder-active silica mixture, asfor example a zeolite for added cracking activity.

When utilized as a catalyst or a catalyst component, the silica gel ofthe invention is employed under conditions known to be effective for theintended purpose. In general, elevated temperatures and/or pressures arerequired. For example, in the cracking of hydrocarbons, elevatedtemperatures above about 900° F. are usually employed. Where ahydrogenation function is also desired, as for example in hydrocrackingor hydrodewaxing, the presence of hydrogen is required, and usually anelevated pressure above about 500 p.s.i.g.

In the following Examples, the preparation of the silica gel of theinvention and processes involving its use as a catalyst are described.The Examples, however, are for the purpose of illustration only and arenot intended to limit the invention, which is defined by the claims.

EXAMPLE I

In this Example, a silica gel is prepared in accordance with theinvention, and its catalytic properties for isomerizing ortho-xylene aredemonstrated.

A solution is prepared having the following components: 512 ml. ofwater, 139 g. of "N" Brand sodium silicate solution (containing 28.9% byweight SiO₂ and 8.9% by weight Na₂ O), 8.7 g. of n-propyl bromide, 8.5g. of n-butyl bromide, 19.1 g. of tri-n-propylamine, and 40.3 g. ofmethylethylketone. The solution is then acidified to a pH of 11.0 by theaddition of 6N acetic acid, after which the solution is allowed to standfor 64 hours at 79° C. A gel forms in the solution, and after separationfrom the mother liquor having a pH of 11.3, the gel is washed withdistilled water, dried, exchanged three times with a solution of 10% byweight ammonium nitrate to remove the exchangeable sodium cations, andfinally calcined in air at 1200° F. for two hours, producing a granularproduct.

The granular silica gel is given the designation Y-2822A and found tohave a surface area of 112 m² /gm. When tested with dicinnamalacetoneand triphenylcarbinol indicators, high acidity is indicated. Inaddition, X-ray diffraction analysis determines that the granules areessentially amorphous in nature and not crystalline. The granules arescreened to collect a 20/40 mesh fraction for catalytic testing.

A comparative experiment is then performed to demonstrate the catalyticactivity of the Y-2822A silica gel, prepared in accordance with theinvention, against a conventional silica gel. The conventional silicagel is Davison No. 12 having a mesh size of 28/40 and a surface area of695 m² /gm. Each gel is then tested as follows: hydrogen andortho-xylene in a 2:1 mole ratio are passed over 1.70 gram samples ofthe silica gels at atmospheric pressure and at a weight hourly spacevelocity of 2.1 in the case of the Y-2822A silica gel and 1.6 for theconventional silica gel. The results obtained at varying operatingtemperatures are summarized in the following Table I:

                                      TABLE I                                     __________________________________________________________________________                              Davison No. 12                                      Catalyst Silica Gel of Invention                                                                        Silica Gel                                          __________________________________________________________________________    Hours on Stream                                                                         1    2   3   4   1    2                                             Operating                                                                              600  700 800 900 700  900                                            Temperature, ° F.                                                      Space Velocity,                                                                        2.1  2.1 2.1  2.1                                                                              1.6  1.6                                            WHSV                                                                          Product Color                                                                          Yellow                                                                             Yellow                                                                            Yellow                                                                            Yellow                                                                            Clear                                                                              Clear                                          Product                                                                       Distribution,.sup.1                                                           m-xylene 0.00 0.27                                                                              4.36                                                                              14.2                                                                              0.00 0.08                                           p-xylene 0.00 0.00                                                                              0.13                                                                               0.66                                                                             0.00 0.00                                           Total Conversion                                                                       0.00 0.27                                                                              4.49                                                                              14.9                                                                              0.00 0.08                                           Specific <0.001                                                                              0.080                                                                            1.33                                                                               4.39                                                                             <0.001                                                                              0.003                                         Rate.sup.2 × 10.sup.10                                                  __________________________________________________________________________     .sup.1 The product distribution is determined as millimoles of product pe     mole of feed.                                                                 .sup.2 The specific rate is a measure of the activity of the catalyst to      promote a given reaction, in this case, the conversion of oxylene to tota     pxylene and mxylene products. The specific rate is an indication of the       number of molecules of reactant which are converted per second per unit       area of surface area of catalyst. In the present case, the specific rate      is calculated by reference to the following equation:                         ##STR1##                                                                      with the resulting value being in terms of the number of molecules of         oxylene converted per second per square centimeter of surface area.      

The data in the foregoing Table I indicate that the silica gel of theinvention is much more highly active than conventional silica, yieldingat 900° F. over 185 times as much para-xylene plus meta-xylene. Theseresults are especially surprising in view of the fact that the silicagel of the invention is prepared with a much reduced surface area and isutilized at a higher space velocity. Both of these features should haveworked to the disadvantage of the Y-2822A silica gel composition, yet itproves far more active for isomerization reactions.

It will also be noted in the data in Table I that, as indicated by thedifferences in specific rates at 900° F., the silica gel of theinvention is more than 1200 times as catalytically active as theconventional silica gel for the isomerization of o-xylene to totalp-xylene and m-xylene products. At 900° F. operating temperature, thespecific rate for the silica gel of the invention for isomerizingo-xylene will usually be such that at least 1.0×10¹⁰, more usually atleast 2.0×10¹⁰, preferably at least 3.0×10¹⁰, and most preferably (asevidenced by the data of Table I) at least 4.0×10¹⁰ molecules ofo-xylene are converted per second per square centimeter of catalyticsurface area.

EXAMPLE II

In this Example, a silica gel prepared in accordance with the inventionis shown to have catalytic cracking activity for converting hydrocarbonsinto lower boiling products.

A sample of the Y-2822A silica gel of the invention, prepared asdescribed in Example I, is utilized in a continuous process for crackinga heavy naphthenic hydrocarbon oil having the following properties:

                  TABLE II                                                        ______________________________________                                        Specific Gravity 60/60   0.89                                                 Initial Boiling Point    580° F.                                       Vol. % Boiling below 700° F.                                                                    4.6                                                  Vol. % Boiling below 1000° F.                                                                   96.6                                                 ______________________________________                                    

The operating conditions are as summarized in Table III:

                  TABLE III                                                       ______________________________________                                        Operating Temperature, °F.                                                                      900° F.                                       Space Velocity, WHSV     8.0                                                  Catalyst to Feedstock Wt. Ratio                                                                        4.0                                                  ______________________________________                                    

The distribution of products obtained are summarized in the followingTable IV, with it being noted that the temperature ranges given for theliquid products are the true boiling ranges for such products atatmospheric pressure.

                  TABLE IV                                                        ______________________________________                                        Gas Production        190 SCF/bbl                                             Light Liquid, x-180° F.                                                                      11.3 vol. %                                             Gasoline, 180°-420° F.                                                                22.0 vol. %                                             Turbine Fuel, 300°-550° F.                                                            12.0 vol. %                                             Furnace Oil, 300°-700° F.                                                             19.3 vol. %                                             ______________________________________                                    

These data clearly indicate that the silica gel of the invention hassubstantial catalytic cracking activity.

In the foregoing discussion, the primary attention has been directed tosilica gels, and this for the reason that silica gel is the preferredform of the amorphous silica of the invention. However, other forms ofamorphous silica may be prepared in accordance with the invention, asfor example precipitated silica. Precipitated silica is an amorphoussilica produced, as its name implies, by a chemical reaction involvingprecipitation, usually as a result of destabilizing an aqueous silicatesolution. Destabilization can be effected by adding flocculents orprecipitating agents which tend to decrease the surface charge onsilica. For example, the reaction mixture may be heated, mixed with aprecipitating agent such as sodium carbonate, and then cooled toprecipitate silica at high pH. Fluoride salts may similarly serve asprecipitating agents, as also may certain water-soluble organic solventssuch as acetone and alcohols, particularly at high pH. In addition,polyvalent cations can be used as flocculating agents to promoteprecipitation. For example, barium and/or calcium can be used toprecipitate fine particles of silica.

In the invention, the foregoing procedure is modified such that theprecipitate is formed in the presence of one or more of the organicreactants hereinbefore described in fuller detail. In other words, thereaction mixture for producing precipitated silica is of similarcomposition to those described hereinbefore with respect to thepreparation of silica gel except that it further contains one or moreflocculating and/or precipitating agents which induce the formation of asilicon-containing precipitate as opposed to a silicon-containinghydrogel. The flocculating and/or precipitating agent is added in anamount sufficient to effect the precipitation, which may occurinstantaneously or require up to about two hours for completion. Afterthe precipitate is formed, it is separated from the mother liquor and,if necessary, washed free of detrimental metals, particularly alkaliand/or alkaline earth metals. The washing may be carried out without anyaqueous solution, but solutions of an acid such as nitric acid or anammonium salt such as ammonium nitrate or ammonium carbonate arepreferred. The washing is preferably carried out to a degree such thatthe precipitate contains less than 0.010 atoms of total alkali andalkaline earth metals to each atom of silicon. The washed precipitate isthen dried and/or calcined to the desired degree of dehydration,resulting in a precipitated silica of the invention.

Although the invention has been described in conjunction withembodiments thereof, including a preferred embodiment, it is apparentthat the invention is capable of many modifications, alternatives, andvariations. For example, in one embodiment of the invention, instead ofpreparing the silica gel from a reaction mixture having a pH between theusual values of 8 and 12, one may prepare the silica gel from reactionmixtures of lower pH, even acidic pH's, such as from about 1 to 5. Thisembodiment of the invention has the advantage of relatively rapidformation of the silica gel, requiring little aging time in mostinstances, and in many others, essentially none. In effect, the gelprecipitates almost as soon as it forms, the rate of formationincreasing with decreasing pH's. Accordingly, it is intended to embracewithin the invention all such modifications, alternatives, andvariations as may fall within the spirit and scope of the appendedclaims.

We claim:
 1. A process for promoting a cracking reaction by contacting ahydrocarbon feed stock under cracking conditions with a catalystprepared by a method comprising forming a hydrogel or precipitate in areaction mixture comprising water, silicate anions and an organicreactant selected from the group consisting of amines having a pK_(a)value above about 10.0, quaternary ammonium cations having a nitrogenatom bonded to four carbon atoms, quaternary phosphonium cations havinga phosphorus atom bonded to four carbon atoms, precursors of theforegoing and mixtures thereof, and dehydrating the resultant hydrogelor precipitate to yield a product containing amorphous silica.
 2. Acracking process comprising contacting a hydrocarbon under crackingconditions with a catalyst prepared by a method comprising forming ahydrogel in a reaction mixture comprising water, silicate anions andquaternary ammonium cations having a nitrogen atom bonded to four carbonatoms, and dehydrating the hydrogel to yield a product containing asubstantial proportion of amorphous silica gel.
 3. A process forpromoting a cracking reaction by contacting organic chemical reactantsunder reaction conditions with a catalyst prepared by a methodcomprising acidifying a reaction mixture comprising sodium silicate,water and a quaternary ammonium cation having a nitrogen atom bonded tofour carbon atoms, allowing a hydrogel to form in the reaction mixture,separating the hydrogel from the reaction mixture and removing one ormore metals from said hydrogel, and dehydrating said hydrogel to producea product containing a substantial proportion of amorphous silica gel.4. The process defined in claim 3 wherein said reaction conditionscomprise an elevated temperature above about 900° F.
 5. The processdefined in claim 3 wherein, prior to said dehydrating of said hydrogel,a cracking component is dispersed into said hydrogel.
 6. A process forpromoting a hydrocarbon cracking reaction by contacting a hydrocarbonunder cracking conditions with a catalyst prepared by a methodcomprising (a) forming a hydrogel in a reaction mixture comprisingwater, silicate anions and a quaternary ammonium cation having anitrogen atom bonded to four carbon atoms, said quaternary ammoniumcation is introduced into said reaction mixture by addition of one ormore precursors thereof, said precursors being selected from the groupconsisting of (1) quaternary ammonium compounds containing a nitrogenatom bonded to four carbon atoms and having at least some solubility inwater and (2) amines or ammonia in combination with an emulsifying agentand one or more alkyl compounds containing a halide or sulfate, saidalkyl compounds being present in an amount at least sufficient to bondat least one nitrogen atom of the amines or ammonia to four carbonatoms, and (b) dehydrating the hydrogel to yield a product containing asubstantial proportion of amorphous silica gel.
 7. In a catalyticcracking process wherein a hydrocarbon feedstock is contacted undercracking conditions with a catalyst, the improvement comprisingemploying as a catalyst a composition prepared by a method comprisingacidifying a reaction mixture comprising sodium silicate, water, and aquaternary ammonium cation having a nitrogen atom bonded to four carbonatoms, said acidification resulting in a pH between 8 and 12 and saidcarbon atoms each being members of alkyl groups containing between 1 and6 carbon atoms, allowing a hydrogel to form in the reaction mixturemaintaindd at a temperature below 95° C., recovering the hydrogel fromthe remainder of the reaction mixture, removing sodium from the hydrogelby washing, dehydrating said hydrogel to produce a product containing asubstantial proportion of silica gel, and admixing a cracking componentinto said silica gel.
 8. The process defined in claim 7 wherein saidcracking component comprises a hydrogen Y zeolite containing one or morerare earth elements.
 9. The process defined in claim 7 wherein saidquaternary ammonium cation is introduced into said reaction mixture inprecursor form, said precursor form comprising a combination of an aminecontaining a nitrogen atom bonded to three carbon atoms plus one or morealkyl halides containing between 2 and 4 carbon atoms.
 10. In acatalytic cracking process wherein a hydrocarbon feedstock is contactedunder cracking conditions with a catalyst, the improvement comprisingemploying as a catalyst a composition comprising an amorphous silicaprepared by a method comprising acidifying a reaction mixture comprisingwater, sodium silicate, and a quaternary ammonium cation having anitrogen atom bonded to four carbon atoms, said acidifying resulting ina pH between about 8 and 12, allowing the reaction mixture to standunder conditions sufficient to produce a hydrogel therein from which anessentially amorphous silica gel is produced in a dehydrating stephereinafter defined, separating the hydrogel from the remainder of thereaction mixture, washing the hydrogel so as to reduce the sodiumcontent thereof, and dehydrating the washed hydrogel to yield a silicaproduct consisting essentially of an amorphous silica.
 11. The processdefined in claim 10 wherein said hydrogel is produced in said reactionmixture at a temperature maintained below 100° C.
 12. The processdefined in claim 10 wherein, prior to said dehydrating of said hydrogel,a cracking component is dispersed into said hydrogel.
 13. The processdefined in claim 12 wherein said cracking component comprises a hydrogenY zeolite containing one or more stabilizing rare earth elements.